US3351557A

US3351557A - Detergent compositions

Info

Publication number: US3351557A
Application number: US514404A
Authority: US
Inventors: James L Almstead; Henry R Greeb; Tom H Ohren
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1964-10-06
Filing date: 1965-12-16
Publication date: 1967-11-07
Anticipated expiration: 1984-11-07
Also published as: NO121799B; FI45206B; NL6617647A; GB1092149A; SE339731B; FR1505726A; FI48284C; FI45206C; CH473216A; DK129096B; FI48284B; DE1467662A1; GB1115300A; BE691077A; SE349319B; DE1467662B2; DE1617184A1

Description

United States Patent Ofi ice 3,351,557 Patented Nov. 7, 1967 ABSTRACT OF THE DISCLOSURE Built liquid detergent emulsions containing certain nonionic detergents, either certain zwitterionic detergents, certain amine oxide detergents or certain phosphine oxide detergents, a detergency builder salt, a polymeric emulsion stabilizer, and water.

This application is a continuation-in-part of copending application Ser. No. 401,975, filed Oct. 6, 1964 and now abandoned.

This invention relates to detergent compositions having superior detergent properties. Specifically this invention relates to built liquid detergent compositions in the form of stable oil-in-water emulsions.

There has been considerable demand for liquid detergent compositions which provide superior detergency under a wide variety of conditions including cool water conditions. In order to obtain superior detergency under a Wide variety of conditions, many components are needed and the formulation of liquid detergent compositions is very diflicult when said compositions contain many different materials, both organic and inorganic. For example, when the liquid detergent composition contains inorganic builders they tend to cause portions of the organic materials to separate into a second phase. Also individual components may react with each other to the detriment of one or both of said components.

It is an object of this invention to provide a built liquid detergent composition which has superior detergency characteristics, including cool water detergency characteristics.

It is a further object of this invention to provide a compatible, multi-component, liquid detergent composition in the form of a stable emulsion.

It is a still further object of this invention to provide a liquid detergent composition which has superior detergency properties with respect to whiteness maintenance.

It is yet another object of this invention to provide mixtures of detergent compounds in a convenient form.

These and other objects can be achieved by providing a built liquid detergent composition, in the form of a stable oil-in-water emulsion, consisting essentially of:

(I) From about 1% to about 15%, preferably from about 3% to about 12%, by weight of a nonionic detergent having the formula wherein R is selected from the group consisting of alkyl radicals containing from about 8 to about 18 carbon atoms and alkyl phenyl radicals wherein the alkyl groups contain from about 9 to about 15 carbon atoms, wherein Y is an integer from 0 to about 7 and wherein Z is an integer from about 5 to about (II) From about 2% to about 10% by Weight of a detergent selected from the group consisting of (a) A sultaine detergent having the formula wherein R is an alkyl radical containing from about 10 to about 18 carbon atoms, R and R are each selected from the group consisting of methyl, ethyl and hydroxy ethyl radicals, R is selected from the group consisting of methylene, ethylene and propylene radicals and X is selected from the group consisting of hydrogen and a hydroxyl group wherein said hydroxyl group is attached only to a secondary carbon atom;

(b) A detergent having the formula wherein R is selected from the group consisting of alkyl and monohydroxy alkyl radicals containing from about 10 to about 24 carbon atoms, containing from 0 to about 3 ether linkages and having one moiety which contains from about 10 to about 18 carbon atoms and no ether linkages; R? and R are each selected from the group consisting of methyl, ethyl, hydroxy ethyl, propyl and hydroxyl propyl radicals and wherein Q is selected from the group consisting of phosphorus and nitrogen atoms; and

(c)Mixtures thereof;

(III) From about 10% to about 36% by weight of builder selected from the group consisting of alkali metal (e.g., sodium and potassium) pyrophosphates; alkali metal, ammonium and substituted ammonium salts of nitrilo triacetic acid, ethane-l hydroxy-l,l-diphosphonic acid, and ethylene-diaminetetraacetic acid; potassium tripolyphosphate; and mixtures thereof, there being no more than about 10% by weight of potassium tripolyphosphate present;

(W) An emulsion stabilizer selected from the group consisting of ethylene/maleic-anhydride copolymers having a specific viscosity of from about 0.5 to about 1.0, said specific viscosity being determined on a 1% solution of the copolymer in dimethyl formamide at 25 C., and methylvinyl-ether/maleic-anhydride copolymers having a specific viscosity of from about 0.1 to about 0.6, said specific viscosity being determined on a 1% solution of the copolymer in methyl ethyl ketone at 25 0.; when the former emulsion stabilizer is used it is present in an 3 amount from about 1% to about 2% by weight and when the latter emulsion stabilizer is used it is present in an amount from about 0.3% to about 1.5% by Weight, and mixtures thereof; and

(V) The balance water, the pH of the composition being between about 11.7 and about 13.0.

The proportions of these ingredients in combination provide both the desired product stability and product performance characteristics.

The pH of the above composition is adjusted to from about 11.7 to about 13.0, if necessary, by the addition of either potassium hydroxide, sodium hydroxide, lithium hydroxide, or the corresponding oxides, for example. All percentages, parts, and ratios herein are by weight unless otherwise specified.

Numerous optional ingredients can be added to the above formula to impart special effects Without substantially modifying the basic desirable detergent characteristics of the composition, including from about 0.1% to about 0.5% of a germicide having the formula wherein R is an alkyl radical containing from about 8 to about 18 carbon atoms, R and R are each selected from the group consisting of methyl, ethyl and propyl radical-s, R is selected from the group consisting of methyl, ethyl and benzyl radicals and X is selected from the group consisting of bromide, fluoride and chloride anions.

The discrete phase, i.e., the oily phase, in the oil-inwater emulsions of this invention contains the nonionic detergents, at least the major portion of the other detergents (II), and it is believed, the major proportion of any minor organic ingredients present, e.g., optical brighteners and pigments. In order for there to be an oily phase, the nonionic detergent must be oily in nature although it need not be an oil (liquid). Examples of suitable nonionic detergents from the class generically defined above include (1) tetrapropylene phenol condensed with about 11 moles of ethylene oxide per mole of tetrapropylene phenol; (2) coconut alcohol condensed with from about to about 8 moles of propylene oxide per mole of coconut alcohol and this reaction mixture condensed subsequently with from about 7 to about moles of ethylene oxide per mole of reaction mixture.

The function of the nonionic detergents is two-fold. First, as hereinbefore described, the nonionic detergents constitute the main component of the oily phase. Secondly, the nonionic detergents impart desirable whiteness maintenance properties to the compositions in their laundering function.

Specific examples of the detergents of Group II include the following:

(a) Sultaine detergents of particular interest are those in which the long alkyl chain (R is a specific C C alkyl or a mixture of alkyl chains derived from naturally occurring substances, whether hydrogenated or not, and the short alkyl chains are methyl groups. For instance, where R is derived from tallow or coconut oil, R is an ethylene radical With a hydroxyl group substituted on the middle carbon atom of the CH2R4 grouping, and R and R are methyl groups, the sultaine detergent is of particular interest. Other specific examples of preferred sultaine detergents include 3 (N,N-dimethyl-N- hexadecylammonio)propane l sulfonate, 2 (N- rnethyl N ethyl N decyl)-ethane 1 sulfonate, 4 (N,N-diethyl N tetradecyl)-butane 1 sulfonate, 4 [N,N-di(2 hydroxyethyl) N octadecyl] 2-hy droxy butane 1 sulfonate, 2 [N,N-di(2 hydroxyethyl)-N-dodecyl1-ethane 1 sulfonate, 4[N-methyl-N- (2 hydroxyethyl) N hexadecyl] 3 hydroxybutane- 1 sulfonate, and 3 (N,N-dimethyl-N-hexadecylammonio) 2 hydroxypropane 1 sulfonate. Other specific examples include compounds wherein different long alkyl chains are used to provide the corresponding decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl homologs of the above compounds such as 3 (N,N-dimethyl-N- tetradecylammonio)propane 1 sulfonate, 3 (N,N- dimethyl-N-octadecylaxnmonio)-ethane 1 sulfonate, etc. Still other specific examples include compounds where the short chains substituted on the nitrogen atom in the above compounds are replaced by the corresponding methyl, ethyl and hydroxy ethyl groups to provide the corresponding homologs of the above compounds.

(b) Specific examples of the phosphine oxide detergents include dimethyldodecylphosphine oxide dimethyltetradecylphosphine oxide ethylmethyltetradecylphosphine oxide cetyldimethylphosphine oxide dimethylstearylphosphine oxide cetylethylpropylphosphine oxide diethyldodecylphosphine oxide diethyltetradecylphosphine oxide dipropyldodecylphosphine oxide bis- (Z-hydroxyethyl dodecylphosphine oxide bis-(2-hydroxyethyl)-3-dodecoxy-2-hydroxypropylphosphine oxide (Z-hydroxypropyl methyltetradecylphosphine oxide dimethyloleylphosphine oxide, and dimethyl-(2-hydroxydodecyl) phosphine oxide The C C dimethyl homologs of the above compounds are preferred. Other examples include those compounds wherein the short alkyl chains in the above compounds are each replaced by the methyl, ethyl, hydroxy ethyl, propyl and hydroxy propyl radicals to form homologs of the above compounds. Still other examples in clude those compounds wherein decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl hydrocarbon groups replace the long alkyl chains in the above compounds to form the corresponding homologs of the above compounds.

(c) Specific examples of the amine oxide detergents include dimethyldodecylamine oxide dimethyletetradecylamine oxide ethylmethyltetradecylamine oxide cetyldimethylamine oxide dimethylstearylamine oxide cetylethylpropylamine oxide diethyldodecylamine oxide diethyltetradecylamine oxide dipropyldodecylamine oxide bis-(2-hydroxyethyl)dodecylamine oxide bis (Z-hydroxyethyl)-3-dodecoxy-2-hydroxypropylamine oxide (Z-hydroxy-propyl)methyltetradecylamine oxide dimethyloleylamine oxide dimethyl-(Z-hydroxydodecyl) amine oxide The C C dimethyl or bis-(Z-hydroxyethyl) homologs of the above compounds are preferred. Other examples include those compounds wherein the short alkyl chains in the above compounds are each replaced by the methyl, ethyl, hydroxy ethyl, propyl and hydroxy propyl radicals to form homologs of the above compounds. Still other examples include those compounds wherein decyl, dodecyl, tetradecyl, hexadecyl and octadecyl hydrocarbon groups replace the long alkyl chains in the above compounds to form the corresponding homologs of the above compounds.

The sultaine, phosphine oxide, and amine oxide detergents impart superior detergency properties to the compositions of this invention. *In particular, the preferred sultaine, amine oxide and phosphine oxide detergents impart cool, as well as hot, water detergency properties to the compositions. It is surprising that these surfactants do not detract from the excellent whiteness maintenance properties of the nonionic detergent surfactants when used in combination with the nonionic detergent surfactant. Sultaine detergents are preferred.

The alkali metal pyrophosphates which form a part of the compositions of this invention are the conventional detergent builders found in built liquid detergent compositions. The preferred pyrophosphate is tetra potassium pyrophosphate.

The preferred organic chelating agents are alkali metal, e.g., sodium or potassium, ammonium, or substituted ammonium salts of nitrilo triacetic acid, or ethane-l-hydroxy- 1,1 diphosphonic acid, preferably the potassium salts. The organic chelating (sequestering) agent in admixture with the pyrophos-phate provides superior whiteness maintenance characteristics for the detergent composition. Ethylenediaminetetraacetic acid salts are efii-cient, but care must be taken that the compositions are used with sufficient corrosion inhibitor to prevent this chelating agent from creating excessive corrosion problems.

As used herein, substituted ammonium salts refer to, for example, monoethanol ammonium, diethanol ammonium, and triethanol ammonium salts.

The above organic chelating agents and pyrophosphates tend to be corrosive to aluminum. Therefore, it is desirable that a corrosion inhibitor be included in the composition if the washing solutions will contact aluminum. Sodium and potassium silicates having a ratio of (M refers to sodium or potassium) from about 1.0 to about 2.6, preferably from about 1.6 to about 2.6 are effective when included at a level of from about 2% to about 4% by Weight. Less than 2% of silicate solids does not provide sufficient protection under more extreme conditions and more than 4% has an adverse effect on product stability.

The emulsion is kept stable by the presence of the aforementioned specific emulsion stabilizers. Apparently the specific compositions described herein, and especially the compositions containing the sultaine detergents hereinbefore described, are extremely sensitive to changes in the stabilizer and therefore the choice of stabilizers is considered to be critical. These stabilizers are described in US. Patent 2,047,398. Preferably these copolymers are linear and the molar ratio of the monomers in these materials is preferably about 1:1. The copolymers are defined herein in terms of their specific viscosities which is the accepted way of defining this type of compound. Wherever specific viscosities are given herein they are based on the tests hereinbefore described with respect to each type of stabilizer.

The presence of these stabilizers appears to be critical to forming the stable emulsion product of this invention. The specific emulsion stabilizers are particularly beneficial With respect to shipment conditions when the compositions are subjected to continuous shocks and agitation.

The pH of the subject compositions must be maintained within the range 11.7 to 13.0. Failure to maintain the pH in this range can be disastrous with respect to product stability. As hereinbefore described, the pH can be adjusted to this level, for example, by the addition of sodium hydroxide, potassium hydroxide, lithium hydroxide, or the corresponding sodium, lithium, and potassium oxides.

Option-a1 ingredients include optical Whitening (brightening) agents. It has been discovered that only a limited number of optical whitening .agents are compatible in the compositions of this invention and particularly when the preferred sultaine detergents are used. Suitable optical brightening agents include at least one optical whitening agent selected from the 'group consisting of:

(1) The reaction product of about one mole of ethylene oxide and one mole of 1,2-bis(benzimidazolyl)ethylene, e.g., N (2'-hydroxyethyl)-1,2-bis(benzimidazolyDethyL ene;

(2) Tetrasodium 4,4 bis[(4"-bis(2"-hydroxyethyl)- amino 6" (3"-sulfophenyl)amino-1",3,5-triazin-2"- yl) amino] -2,2' stilbendedisulfonate;

b (3) N (2-hydroxyethyl-4,4-bis(benzimidazolyl)stilene;

(4) Disodium-4-(6'-sulfonaphtho[1',2'-d]triazol-2-yl)- Z-stiIbenesulf-onate;

(5) Disodium 4,4'-bis[(4"-(2"-hydroxyethylamine)- 6"-anilino- 1 ",3 ",5 -triazin-2'-yl) amino] 2,2-stilbenedisulfonate;

(6) Disodium 4,4 bis[(4"-(2"'-hydroxyethoxy)-6" anilino 1,3,5"-triazin-2"-yl)amino]-2,2-stilbenedisulfonate;

(7) 1,2-bis 5 '-methyl-2'-benzoxazolyl ethylene;

(8) 4-methyl-7-dimethylaminocoumarin;

(9) 2-styrylnaphth[1,2-d]oxazole;

(10) The reaction product of one mole of 4,4'-bis- (benzimidazolyl)stilbene with about 0.5 mole of ethylene oxide and 0.5 mole of propylene oxide; and

(11) Mixtures thereof.

When the compositions of this invention contain a quaternary ammonium salt, e.g., a quaternary ammonium germicide, nonionic optical whitening agents are preferred. However, the other named ionic optical whitening agents can be used and are desirable, preferably in combination with nonionic optical whitening agents.

These optical whitening agents are used in a level of from about 0.03% to about 0.8% and preferably at a level of about 0.4% by weight. They are normally added to, and are present in, the discrete, e.g., oily, phase of the composition.

It is a particular advantageous feature of this invention that the above brighteners (optical Whitening agents) in the oily phase of the composition are considerably more compatible with the sultaine, phosphine oxide and amine oxide detergent surfactants (as well as cationic materials when they are present) when the composition is in the form of an oil-in-water emulsion as herein described, rather than a homogeneous aqueous solution.

The compositions can also contain from about 0.2% to 1.5% of soil suspending agents selected from the group consisting of alkali metal, ammonium and substituted ammonium carboxymethylcellulose and alkali metal, ammonium and substituted ammonium carboxymethylhydroxyethylcellulose. It is an advantage of the liquid detergent compositions of this invention that the more readily available carboxymethylcellulose salts can be used. The salts of car-boxymethylcellulose are less soluble than the salts of carboxymethylhydroxyethylcellulose and it is normally very difficult to use c-arboxymethylcellulose salts in liquid detergent compositions. By suspending the carboxymethylcellulose salts in the discrete phase, the problem of solubility is avoided. The carboxymethylcellulose can also be added by dissolving it in a silicate-water solution prior to adding it to the composition.

Other optional ingredients include the germicides hereinbefore mentioned. Specific examples of such germicides include pentadecyl benzyl dimethyl ammonium chloride and tetradecyl diethyl methyl ammonium bromide.

The compositions of this invention can be prepared by the following steps:

(I) A pre-mix is formed containing the nonionic detergent surfactant; at least approximately one-fourth of the sultaine, phosphine oxide or amine oxide detergent surfactant; the optical whitening agents; the dyes, the carboxymethylcellulose and any caustic required to make the solution alkaline. These ingredients are mixed thoroughly.

(II) The emulsion stabilizer is prepared by hydrolyzing the copolymer described hereinbefore. A small amount of the nonionic detergent, about 2% to 80% by weight based on the amount of the unhydrolyzed emulsion stabilizer, is dissolved in water and then mixed with the emulsion stabilizer. The mixture is heated to from about 150 F. to about 200 F. to permit the emulsion stabilizer to hydrolyze which brings the pH down below 7. It is believed that the nonionic detergent surfactant reacts with the emulsion stabilizer to form an ester. The amount of nonionic detergent surfactant which is utilized in the hydrolysis of the emulsion stabilizer is very important since relatively minor changes in the amounts of the nonionic detergent surfactant cause very large changes in the viscosity of the final product. The use of larger amounts of nonionic detergent surfactant raises the viscosity.

(III) The hydrolyzed resin is made alkaline, preferably with either sodium hydroxide or potassium hydroxide.

(IV) The pro-mix and the aqueous solution containing the hydrolyzed emulsion stabilizer are mixed together. Preferably at least a portion of the builder is added to the aqueous solution containing the emulsion stabilizer before the pre-mix is added to the aqueous solution.

(V) The rest of the sultaine, phosphine oxide or amine oxide detergent surfactant, if any, is added to the mixture. (VI) Any additional builder is added to the mixture.

(VII) The silicate, if any, is added to the composition.

(VIII) In each of the preceding addition steps the composition is mixed very thoroughly after each addition. At this point, however, while the temperature of the composition is relatively high, the composition is mixed by a high shear method, e.g., with an impeller having a tip speed of greater than 2500 feet per minute. High shear mixing improves the stability of the emulsion by reducing the size of the droplets of the dispersed phase.

(IX) The composition is cooled and perfume is added.

The compositions of this invention can also be prepared by mixing any optical brightener included, any soil suspending agent, e.g., sodium carboxymethylcellulose, included, the nonionic detergent surfactant, the sultaine, phosphine oxide or amine oxide detergent surfactant and the pigment, if any. This mixture forms the dispersed (oily) phase of the emulsion. This dispersed phase is added to a solution of the emulsion stabilizer prepared as hereinbefore described and sodium acid pyrophosphate (or potassium acid pyrophosphate) in water and mixed thoroughly.

Potassium or sodium hydroxide is then added as necessary to neutralize the sodium acid pyrophosphate; the other ingredients, e.g., the potassium nitrilo triacetate, potassium or sodium pyrophosphate, sodium silicate, etc., are added to this mixture.

The compositions of this invention are highly effective cleaning compositions. As used herein, cleaning ability is the ability of a solution of a detergent composition to remove soil from cloth. Whiteness maintenance relates to the ability of a detergent solution to prevent suspended soil from depositing on the cloth during the washing operation. The term detergency as used herein, is included to embrace both cleaning ability and whiteness maintenance. The detergent compositions of this invention are particularly effective insofar as whiteness maintenance is con- Cerned.

The compositions of this invention are particularly effective under cool water washing conditions, e.g., from about 80 F. to about 100 F. This is especially true when the sultaine detergents are present in the compositions of this invention.

The practice of this invention is demonstrated by the following examples.

EXAMPLE I Liquid detergent compositions were prepared in the form of stable oil-in-water emulsions and having the following formulas (all iipures are percent by weight of the 0 compositions). They were prepared by mixing the optical brightener, the soil suspending agent, the nonionic detergent and the other detergent, and the pigment. This mixture was added to an aqueous solution of the emulsion stabilizer and sodium acid pyrophosphate and mixed thoroughly. The potassium hydroxide was added to bring the pH to 12 and other ingredients were then added with mixing.

Compositions Do-rlecyl-phenol:ethylene-oxide condensate containing an average of about 11 moles of ethylene oxide per mole of phenol 5. 4 6 3-[. I-ulkyl-N,Ndimothyl arnrnonio1-2d1ydroxypropane-l-sulionate; the alkyl being derived from coconut alcohol and being 2% C10, 66% C12,

23% C14, 9% Cm 5. 4 6 Potassium pyr0phosphate 27 20. 2 Potassium nitrilo triaeetate 8. 3 6. 25 Sodium silicate (2.45:1; SiOzINagO 2. 8 2.82 Sodium earboxymethylcellulose. 0.7 0. 7 N-(l-hydroxyethyD-l,2-bis (benzimidazolyl) ethylene 0.005 0.005 Tetresodium 4,4-bis[(4-hydroxyethyl)amino- 2-yl)a1nino] 2,2-stilbenedisultonate 0. 15 0. 15 Color Trace Trace Ethylene/maleic-anhydride linear copolymer (1:1) having a specific viscosity of approximately 0.6 (DX 840-21 Resin) 1. 4 1. 4 POCIUIIIO 0.3 0.3 Water Balance Balance These compositlons were excellent detergents and had good whiteness maintenance properties in fabric launder- When a coconut-alcohol ethylene-oxide condensate containing an average of approximately 15 moles of ethylene oxide per mole of coconut alcohol is substituted, either wholly or in part, for the dodecyl-phenol ethylene-oxide condensate in the above compositions, substantially similar results are obtained in that the compositions still have good Whiteness maintenance properties and are excellent detergents.

When coconut alkyl dimethyl phosphine oxide, coconut alkyl dimethylamine oxide, or any of the specific detergents listed on pages 6, 7, 8 and 9, or mixtures thereof are substituted, either wholly or in part, for the 3-(N-alkyl- N,N-dimethylammonio -2-hydroxypropane-l-sulfonate in the above formulas substantially similar results are obtained in that stable emulsion products are obtained having good detergent characteristics.

When methyl-vinyl-ether/maleic-anhydride linear copolymer having a specific viscosity of approximately 0.2 is substituted for the ethylene/maleic'anhydride copolymer in the above formulas, either wholly or in part, substantially similar results are obtained in that the emulsion is stabilized.

When potassium acid pyrophosphate is substituted for part or all of the sodium acid pyrophosphate in the above example, substantially equivalent results are obtained in that the compositions are stable.

In the above formulas, the bulk of the potassium pyrophosphate, potassium nitrilo triacetate, and sodium silicate is in the aqueous phase and the bulk of the other ingredients is in the oil phase. The carboxymethylcellulose and the ethylene/maleic anhydride copolymer are thought to be concentrated at the oil-water interface.

EXAMPLE II The following liquid detergent compositions, when prepared by the method of Example I in the form of stable oil-in-water emulsions are excellent detergent compositions.

Compositions, Percent by Weight C D E Dodeeyl-phenol:propylene-oxide:ethyleneoxide condensate containing an average of 3 moles of propylene oxide and 12 moles of ethylene oxide per mole of phenol 4 6 8 3-(N ,N-dihydroxysthyl-Nhexadecylam1no' nio)propane1-su1fonatc 8 Cocogut alkyl di-(2-11ydroxyethyl)phosphine 6 xi Coconut alkyl di-(Z-hydroxyethybaminc oxide Potassium pyrophosphate Potassium ethylenediaminetetraaceta Potassium nitrilotriacetate 1 Mcthyl-vinyl-cthor/maleic-aiiliydride linear 0 copolymer (1:1) having a specific viscosity of approximately 0.3 (Gantrez AN 119) 1. 5 1. 5 1.5 N-(2-hydroxyethyl iA bis(benzimidazolyl) stilb 0. 05 0.05 0.05 Sodium carboxy yethylcellulose. 0. 7 0. 7 0. 7 Pigments Trace Trace Trace Water Bal Bal Del.

The pH is adjusted to 12 with potassium hydroxide.

In the above examples, the potassium pyrophosphate and the potassium ethylenediaminetetraacetate are predominantly in the aqueous phase and the bulk of the rest of the ingredients is in the oil phase. The oarboxymethylcellulose and the methyl-vinyl-ether/maleic-anhydride copolymer are thought to be concentrated at the oil-water interface.

When, in the above examples, the following brighteners are added in amounts of about 0.4% and/or substituted wholly or in part for the above brighteners substantially equivalent results are obtained in that the compositions are excellent detergents possessing fabric softening properties and having good whitening powers:

(1) The reaction product of about one mole of ethylene oxide and one mole of 1,2-bis(benzimidazolyl)ethylene, e.g., N-(2-hydroxyethyl)-l,3 bis(benzimidazolyl) ethylene;

(2) Tetrasodium 4,4-bis[(4" bis( 2" hydroxyethyl) amino-6"-(3""-sulfophenyl)amino-l",3,5-triazin 2"- yl) amino] -2,2-stilbenedisulfonate;

(3) N (2-hydroxyethyl)-4,4-bis(benzimidazolyl)stilbene;

(4) Disodium-4-(6'-sulfonaphtho[1',2'-d]triazol-2-yl)- Z-stilbenesulfonate;

(5) Disodium 4,4 bis [4"-(2"'-hydroxyethylamine)- 6-anilino-l", 3", 5"-triazin-2"-yl)amino]-2,2-stilbenedisulfonate;

(6) Disodium 4,4-bis[4-(2'-hydroxyethoxy)-6"-anilino l",3",5"-triazin-2"-yl)amino]-2,2-stilbenedisulfonate;

(7) 1,2-bis (5'-methyl-2-benzoxazolyl)ethylene;

(8) 4-methyl-7-dimethylaminocoumarin;

(9) 2-styrylnaphth l ,2-d] oxazole;

(10) The reaction product of one mole of 4,4-bis-(benzimidazolyl)stilbene with about 0.5 mole of ethylene oxide and 0.5 mole of propylene oxide; and

(11) Mixtures thereof; in, e.g., 1:1 ratios by weight.

When in the above examples either the sodium, ammonium, ethanol ammonium, diethanol ammonium, or triethanol ammonium salts of ethane-l-hydroxy-1,1-diphosphonic acid, nitrilotriacetic acid, pyrophosphoric acid, ethylenediaminetetraacetic acid, or mixtures thereof; or potassium ethane-1-hydroxy-1,l-diphosphonate or tripolyphosphate 10%); or mixtures thereof are substituted either wholly or in part for the potassium ethylenediaminetetraacetate and/or potassium nitrilotriacetate in the above compositions, substantially equivalent results are obtained in that the calcium ions, etc., are sequestered.

When pentadecyl benzyl dimet-hyl ammonium chloride and/or tetradecyl diethyl methyl ammonium bromide are added to the compositions of the above examples at levels 10 of about 0.3%, substantially equivalent results are obtained in that the compositions are stable oil-iu-water emulsions and are excellent detergent compositions. In addition, the compositions possess germicidal properties.

When, in the above examples, sodium pyrophosphate is substituted for the potassium pyrophosphate and/or ammonium, monoethanol ammonium, diethanol ammonium, triethanol ammonium, or potassium carboxymethylhydroxyethylcellulose and/ or carboxymethylcellulose are substituted for the sodium carboxymethylhydroxyethylcellulose, either Wholly or in part, substantially equivalent results are obtained in that the above compositions are excellent detergents.

What is claimed is:

1. A built liquid detergent composition, in the form of a stable oil-in-Water emulsion, consisting essentially of:

(I) From about 1% to about 15% by weight of a nonionic detergent having the formula wherein R is selected from the group consisting of alkyl radicals containing from about 8 to about 18 carbon atoms and alkyl phenyl radicals wherein the alkyl groups contain from about 9' to about 15 carbon atoms, wherein Y is an integer from 0 to about 7 and wherein Z is an integer from about 5 to about 45;

(II) From about 2% to about 10% by weight of at least one detergent surfactant selected from the group consisting of (a) A sultaine detergent having the formula atom; (b) A detergent having the formula e E il-)0 1' wherein R is selected from the group consisting of alkyl and rnonohydroxyalkyl radicals containing from about 10 to about 24 carbon atoms, containing from 0 to about 3 ether linkages and having one moiety which contains from about 10 to about 18 carbon atoms and no ether linkages; and R and R are each selected from the group consisting of methyl, ethyl, hydroxy ethyl, propyl and hydroxy propyl radicals, and Q is selected from the group consisting of phosphorus and nitrogen atoms; and (c) Mixtures thereof:

(III) From about 10% to about 36% by weight of builder selected from the group consisting of alkali metal pyrophosphates; the alkali metal, ammonium and substituted ammonium salts of nitrilo triacetic acid, ethane-I-hydroxy-l,l-diphosphonic acid, and ethylenediaminetetraacetic acid; potassium tripolyphosphate; and mixtures thereof, there being no more than about 10% by Weight of potassium tripolyphosphate present;

(IV) An emulsion stabilizer selected from the group consisting of ethylene/maleic-anhydride copolymers having specific viscosities of from about 0.5 to about 1.0 and methyl-vinyl-ether/maleic-anhydride copolymers having specific viscosities of from about 0.1 to

about 0.6; when the former emulsion stabilizer is used wherein R is an alkyl radical containing from about 8 to about 18 carbon atoms, R and R are each selected from the group consisting of methyl, ethyl and propyl radicals, R is selected from the group consisting of methyl, ethyl and benzyl radicals and X is selected from the group consisting of bromide, fluoride and chloride anions.

3. The composition of claim 1 containing as an additional ingredient and present in the oily phase from about 0.03% to about .8% of at least one compatible optical whitening agent selected from the group consisting of:

(1) The reaction product of about one mole of ethylene oxide and one mole of 1,2-bis(benzimidazolyl) ethylene, e.g., N-(2'-hydroxyethyl)-1,2-bis (benzimidazolyl) ethylene;

(2) Tetrasodium 4,4 -bis[4"-bis(2"'-hydroxyethyl)- amino 6-(3-sulfophenyl)amino-1,3",5"-ttriazin- 2-yl amino] -2,2-stilbenedisulfon=ate;

(3) N (2-hydroxyethyl-4,4-bis(benzimidazolyl)stilbene;

(4) Disodium-4-(6'-sulfonaphtho[1',2-d]triazol-2-yl)- 2-stilbenesulfonate;

(5) Disodium 4,4'-bis[(4"-(2'-hydroxyethylamine)- 6" anilino 1",3",5-triazin-2"-y1)amino]2,2-stilbenedisulfonate;

(6) Disodium 4,4-bis[4"-(2"'-hydroxyethoxy)-6"- anilino-1,4",5-triazin-2"-yl) amino] -2,2'-sti1benedisulfonate;

(7) 1,2-bis 5 '-1nethyl-2'-benzoxazoly1 ethylene;

(8) 4-methy1-7-dimethylaminocoumarin;

(9) 2-styrylnaphth[1,2-d]oxazole;

(10) The reaction product of one mole of 4,4-bis- (benzirnidozolyl)stilbene with about 0.5 mole of ethylene oxide and 0.5 mole of propylene oxide; and

(11) Mixtures thereof;

in, e.g., 1:1 ratios by weight.

4. A built liquid detergent composition consisting es sentially of (1) About 5.4% of a dodecyl-phenol ethylene-oxide condensate containing about 11 moles of ethylene oxide per mole of phenol;

(2) About 5.4% of 3-(N,N-dimethyl-N-alkylammonio)-2-hydroxypropane-l-sulfonate wherein said alkyl group contains from about 10 to about 16 carbon atoms and at least about of said groups contain 12 carbon atoms;

(3) About 27% potassium pyrophosphate;

(4) About 8.3% potassium nitrolo triacetate;

(5 About 2.8% sodium silicate having a ratio SiO INa O of about 2.45: 1;

(6) About 0.7% sodium carboxymethylcellulose;

(7) About .2% of compatible brightener selected from the group consisting of 1-benzimidolyl-2-(N-hydroxyethy1)benzimidazolyl ethylene and tetrasodium 4,4- bis[(4 diethanol arnino 6 (3-sulfo) analino-1,3,5 triazine-Z-yl amino] 2,2'-stilbenedisulfonate;

(8) About 1.4% ethylene/maleic-anhydride copolymer having a specific viscosity of approximately 0.7;

(9) About 0.3 coloring matter and perfume; and

(10) The balance water, the pH being adjusted to 12.

References Cited UNITED STATES PATENTS 2,047,398 7/1936 Voss et al. 2602 2,702,277 2/1955 Kinney 252106 X 3,060,124 10/1962 Ginn 252137 X 3,213,030 10/1965 Diehl 252-152 3,216,944 11/1965 Frederickson 252152 X FOREIGN PATENTS 663,565 12/1951 Great Britain. 841,189 7/ 1960 Great Britain.

LEON D. ROSDOL, Primary Examiner.

S. E. DARDEN, Assistant Examiner.

Claims

1. A BUILT LIQUID DETERGENT COMPOSITION IN THE FORM OF A STABLE OIL-IN-WATER EMULSION, CONSISTING ESSENTIALLY OF: (I) FROM ABOUT 1% TO ABOUT 15% BY WEIGHT OF A NONIONIC DETERGENT HAVING THE FORMULA